JPH0218458A - Azlene dye having urethane group and preparatory product thereof and optical recording medium - Google Patents

Abstract

NEW MATERIAL: A compound represented by formula I [L is a (phenyl- substituted) 1-12C alkylene; R¹ is a 1-20C alkyl, a 5-7C cycloalkyl, a (substitutional) phenyl; R²-R⁵ are each H, a halogen, a 1-12C alkoxy, a (substitutional) phenyl, a 1-10C alkoxycarbonyl, a cyano-substituted 1-12C alkyl, etc.].

EXAMPLE: A bis [O-propyl-3-(7-isopropyl-1-methyl-azulene-4-yl)-N-(n-butyl)- urethane]-square acid dye.

USE: A dye for optical-information-recording support, etc.

PROCESS: For example, a urethane-group-containing azulene derivative represented by formula II, prepared by reacting a hydroxyazulene derivative with an isocyanate compound, is reacted with a square acid represented by formula III in a solvent under heating to obtain a compound of formula I.

COPYRIGHT: (C)1990,JPO

Description

Detailed Description of the Invention (In the formula, c is optionally substituted with a phenyl group, 4
C12-alkylene group, R1 is 01-C20-alkyl group, C2-C7-cycloalkyl group or optionally substituted phenyl group, R2, R3, R4 and R5 may be the same or different (independently of each other) Each hydrogen atom or optionally a halogen atom, a C0-C12-flukoxy group, a phenyl group, a substituted phenyl group, a C1-Cl
means a C, -C,□-alkyl group substituted with a 2-alkoxycarbonyl group or a cyano group, provided that R5
means a hydrogen atom, the ring positions of the substituents CH2-L-0-Co-NHR' and R4 may be exchanged with each other within the azulene ring in one or both azulene rings. The present invention relates to an azulene quartz dye having urethane groups, its pre-products and an optical recording medium containing this new dye.

In order to produce optical information recording supports cost-effectively, it is necessary to use dyes with special properties. The dye must meet the following requirements:

1. exhibiting strong absorption between 700 and 900 nm in order to provide a layer writable by a semiconductor laser;

In order to make do with a simple layer configuration (without reflective layer), high reflectivity in the near-infrared region (700-900 nm) should be exhibited within the layer.

High solubility so that thin layers for storage can be formed on a support, for example by spin coating. And it has high stability in one thin layer.

The previously known storage materials have drawbacks in at least one of the above requirements.

It was therefore an object of the present invention to provide new dyes which do not have the above-mentioned disadvantages or only to a very small extent.

For this purpose we have found the azulene quartz dyes of the formula I, which have been characterized in detail above.

All alkylene and alkyl groups shown in Formula I above may be linear or branched.

If a substituted phenyl group is present in formula I, substituents include, for example, C,% C4-alkyl group, 01-C
Examples include 4-alkoxy group and halogen atom.

...Fluorine, chlorine or bromine is preferable as the rogene.

The base is, for example, methylene, ethylene, 1,2- or 1,
3-propylene, 1.2- 1.3- 2.3- or 1
, 4-butylene, pentamethylene, hexamethylene, hebutamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, totecamethylene, phenylethylene, 1-phenyl-1,2-7'ropylene, or 2-phenyl-1,6- It is propylene.

Groups R1, R2, R3, R4 and R5 in formula (1) are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, S-butyl, t-butyl, pentyl, isopentyl, neopentyl, t-pentyl, 2-methylbutyl, Hexyl, 2-)t Chi/L/ He:y Chi/L
/ , heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.

The radical R' can furthermore be, for example, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohentyl, cyclohexyl, cycloheptyl, phenyl, 2- or 4-methylphenyl, 2- or 4-methoxyphenyl, 2- or 4-chlorophenyl or 2,4-dichlorophenyl.

The groups R2, R3, R4 and R5 are furthermore the following groups:

For example, fluoromethyl, chloromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, 2-fluoroethyl, 2-chloroethyl, 2-70 moethyl, 1.1.1-)lifluoroethyl, heptafluoropropyl, 4-10 loftyl. , 5-fluoropentyl, 6-10lohexyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 2-cyanobutyl, 4-
Cyanobutyl, 5-cyanopentyl, 6-cyanohexyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 6-medoxypropyl, 2- or 3- Ethoxyethyl, 4-ethoxybutyl, 4-isopropoxybutyl, 5-ethoxypentyl, 6-medoxyhexyl, benzyl, 1-phenylethyl, 2-phenylethyl, 4-chlorobenzyl, 4-methoxybenzyl, 2-( 4-methylphenyl)ethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 6
-Medoxycarbonylprobyl, 6-nitoxycarbonylprobyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, 5-methoxycarbonylpentyl, 5-ethoxycarbonylhentyl, 6-medoxycarbonylhexyl or 6-methoxycarbonylbutyl Toxicarponylhexyl.

Preference is given to azulene tetraquaric dyes of formula I in which R2, R3, R4 and R5 are each 01-C0-alkyl groups.

Further preferred is an azulene tetragonal dye of the formula (3) in which R1 represents an 01-C11l-alkyl group or a cyclohexyl group.

Particularly preferred is an azulene quartz dye of the formula (2) in which R2 and R4 each represent a methyl group, R3 and R5 each represent a hydrogen atom, and L and R1 each have the above meanings. These dyes are represented by the following formula.

More particularly preferred are formulas l in which R2 and R4 each represent a hydrogen atom, R3 represents an isopropyl group, R5 represents a methyl group, and L and R1 each have the abovementioned meanings.
It is an azulene tetrachloride dye.

These dyes are represented by the following formula.

The dyes of the formula I are obtained from azulene derivatives (1) in which L, R', R2, R3, R4 and R5 each have the meanings given above, by reaction with a square acid of the formula (2) according to the reaction scheme below.

In the case of an azulene derivative of the formula (3) in which R5 represents a hydrogen atom, a bond with a square acid can be formed at various positions of the 5-membered ring, and as described above, the substituent CH2-L-0-C
Isomeric products are formed in which the positions in the ring of o-NH-R' and R4 are exchanged with each other.

That is, here the substituent CH2-L-0-Co-NH-R'
Compounds that form a bond with tetralic acid on the side to which substituent R4 is bonded are distinguished from compounds that form a bond with tetranic acid on the side to which substituent R4 is bonded. These isomeric compounds can be separated by chromatography. However, for use in storage layers, isomer mixtures are usually utilized.

The manufacturing method is known per se, for example Angew.

Chem, 78.937 (j 966 ) + or in the old German patent publication DE-A 3733173.

The present invention further provides the following formula (wherein, 01-C is optionally substituted with a phenyl group)
1□-alkylene group, R1 is a 01-C2G-alkyl group, a C5-C1-cycloalkyl group, or an optionally substituted phenyl group, and R2, R3, R4 and R5 may be the same or different, and each independently a hydrogen atom or optionally a halogen atom, a C,~Cl2-alkoxy group, a phenyl group, a substituted phenyl group, a C8-
The present invention relates to an azulene having a novel urethane group represented by a C12-alkoxycarbonyl group or a C1-Cl2-alkyl group substituted with a cyan group.

Representative examples of the groups R', R2, R3, R4 and R5 are listed above.

Azulene derivatives of the formula (1) having urethane groups are obtained, for example, starting from the corresponding hydroxyalkyl azulene derivatives. The preparation of this product is described, for example, in the old German patent publication DE-A 37 33 173.

Particularly suitable for the reaction are azulene derivatives represented by 1, for example ---(in the formula, the characters have the meanings given above).

As a reaction participant for the hydroxyalkyl azulene derivative, a monoisocyanate represented by the formula % ( ) (in which R1 has the above-mentioned meaning) is used.

The reaction between the hydroxyalkyl azulene derivative and the organic monoisocyanate is carried out by a method known per se. For this purpose, for example, hydroxyalkyl azulenes are prepared with an organic monoisocyanate in an inert solvent (for example methylene chloride, 1,1.2=trichloroethane, doluol, ligroin or cyclohexane) at a temperature of 20 to 60 DEG C., optionally with a catalyst ( For example, the reaction is carried out in the presence of a tertiary amine, a tetraalkylammonium hydroxide or an organotin compound). Generally, incyanate is used in excess.

Another object of the invention is to provide a storage layer with high stability, which can be produced with simple means, which has good writing and good reading (the signal-to-noise ratio should be as high as possible). The object of the present invention was to provide a novel optical recording medium using an azulene tetranic acid derivative as a storage material.

The invention is further characterized in that it consists of a support and a light-sensitive laminar coating containing a dye and optionally a binder, the dye being a dye of formula I according to the first claim.
It is an optical recording medium.

R2, R3, R4 and R5 are each C,% C,-7
Preference is given to optical recording media containing azulene quartz dyes of the formula I denoting a k-kyl group.

Preference is furthermore given to optical recording media containing azulene tetraquaric dyes of the formula I in which R2 means a C0-C1,-alkyl group or a cycloalkyl group.

Particularly preferred is that R2 and R4 each represent a methyl group, and R3 and R5 each represent a hydrogen atom. This is an optical recording medium containing an azulene tetrachloride dye of formula (2).

Particularly preferred is an optical recording medium containing an azulene tetragonal dye in which R2 and R4 are each a hydrogen atom, R3 is an isopropyl group, and R5 is a methyl group.

As the support, preferably a transparent support such as glass or synthetic resin is used. Suitable synthetic resins are, for example, poly(meth)acrylates, polycarbonates, polyesters, epoxides, polyolefins (eg polymethylpentene), polyamides, polyvinyl chloride, polystyrene or polyvinyl esters.

Preferred recording media have a support made of polycarbonate or poly(meth)acrylate, especially polycarbonate.

Furthermore, optical recording media containing 1 to 30% by weight of binder relative to the dye are preferred.

The novel azulene quartz dyes of formula (1) exhibit good optical properties. Furthermore, in the case of the new compounds, the pure dye layer is very stable. That is, recrystallization of a pure dye layer has not been recognized so far, and therefore the addition of a polymeric binder can also be omitted. Furthermore, the light fastness (stability) is also significantly higher than that of known methine dyes, so that the addition of stabilizers to the layer-forming formulation can be kept to a minimum. It is also particularly advantageous that the new dye ■ is well soluble in almost all organic solvents, so that it can be applied directly (without a protective layer).
It can be centrifugally applied onto structural synthetic resin substrates, particularly polycarbonate substrates.

As mentioned above, the solution to be centrifugally coated preferably contains a binder in order to ensure good long-term stability of the recording medium and in particular to be able to optimize the viscosity of the solution to be centrifugally coated. In this case, the solution preferably contains 1 to 30% by weight of binder, based on the amount of dye dissolved in the centrifugal application solution. Examples of the binder include the following. Polyorganosiloxane, epoxide, poly(meth)acrylate, styrene homopolymers and copolymers,
Polyvinylcarbazole, polyvinylpyrrolidone, imidazole copolymer, vinyl ester copolymer, vinyl ether copolymer, vinylidene chloride copolymer, acrylonitrile copolymer, polyvinyl chloride and its copolymer, cellulose acetate or nitrocellulose .

Preferred recording media contain binders based on vinylpyrrolidone-vinyl acetate copolymers or polyvinyl chloride-vinyl ether copolymers.

The optical recording medium of the present invention is preferably produced by centrifugal coating of a solution containing an organic solvent, an azulene quartz dye (1), and optionally a binder. In this case, preferably the centrifugal application solution contains from 1 to 30% by weight of dye, based on the solution.

Suitable solvents are, for example, propatool, ingropanol, butanol, diacetone alcohol, methyl ethyl ketone, doluol, fromoform, L1,2-)lichloroethane or mixtures thereof.

Optionally, the solution may contain up to 10% by weight, based on the content of dissolved dyestuff in the centrifugal application solution, of additives such as antioxidants, doublet oxygen absorbers or UV absorbers.

Preferably, the centrifugal coating solution contains a mixture of two or more antioxidants, doublet oxygen absorbers and UV absorbers up to 5% by weight, based on the amount of dye dissolved in the centrifugal coating solution. Antioxidants absorbing in the near-infrared region, such as DE-A 3505750, DE-A 3505751 or Kim.

Matsuoka, Yomoto, Tsuchiy
Dyes and Pigment by a and Kitao
When using the nickel dithiol complex compounds etc. described in S+ 81381-388 (1987),
Preferably 10 for the content of dissolved dye in the coating liquid.
% by weight.

In this case, centrifugal application is the application of the solution onto a rotating support, preferably having a circular shape. However, it is also possible to first apply the solution to a stationary support and then rotate the support. The supply of the solution onto the support can advantageously be carried out by means of a sprayer or capillary tube or by means of a mechanical pump.

Rotation of the support is generally carried out at a speed of 50-7000 fill, preferably 500-5000 r%, in which case centrifugation of the solution is carried out at a relatively low rotational speed (approximately 500-2000 r%).
pl), followed by a relatively high rotational speed (approximately 5,000 to 7
Centrifugal drying is performed at 000 rpm). The thickness of the layer sensitive to laser light is from 40 to 160 nm, preferably from 80 to 12 nm.
It is within the range of 0 nm. The layer thickness depends on the rotational speed, the concentration and viscosity of the centrifugal coating solution, and the temperature.

In the optical recording medium according to the invention, the layer sensitive to laser light is present in the form of a homogeneous, thin, smooth layer of high optical quality. Therefore, reflectance values are generally in a range greater than 12%.

The novel recording medium is furthermore sufficiently photosensitive to the wavelength of the laser light source used, i.e. it does not form pores when injected with a pulsed beam with an energy content of a few nJ focused at a focal diameter of less than 1 μm. , an excellent signal-to-noise ratio can be obtained.

As a laser light source, solid-state injection lasers emitting near-infrared radiation are preferred due to their small component size, low energy requirements, and the ability to directly modulate the optical output by modulating the operating current. -7 to 1%
AlGaA operating within the wavelength range of oo~900 nm
S lasers are particularly suitable.

Example 1 Production of N-(n-butyl)-〇-propyl-3-[7-isoprobyl-1-methylazulen-4-yl]-urethane (compound/162): Methylene chloride 100
To a solution of 9.6.9 (0.04 mol) of 7-isopropyl-1-methyl-4-(5-hydroxypropyl) azulene in
0.15 mol) was added dropwise at room temperature and the reaction solution was then heated under reflux for 5 hours. The solvent was then distilled off and the residue was subjected to silica gel chromatography (methylene chloride/
acetone).

7. The above-mentioned urethane is a blue high viscosity clear material (Compound 2). OF (51%) was obtained.

Physical data: IR (KBr): I/=4336 (broad,
NH), 2958.2961.2871.1699s (
C=O), 1527.1465.1687.1251.
1142.1061.1030.784crn-”; 'H-NMR (CDCl, ): δ=0,90t(3
H), 1.25-1.55m, 1.38d (6H),
2.17q (2H), 2.66s (3H), 3.0
8q (IH), 3.17m, 4.5t (2H), 4
o46broad (NH), 6.98d (IH), 7
．． 28d (IH), 7.39d (IH), 7.61d (
IH), 8.18s (IH); I3C-NMR (CDC
1,): δ=12.86.13.69.20.00
゜24.75 (2C), 30.79.32.34.34
．． 65.3844.41.04.64.71.112.
40.124.51.125.44.133.26.1
! 15.15.136.48.136.59.137.
41.140.02.147, 92.156.82; MS: m/e=541 (100%), Me>, 326
．． 612.298.258.240.224 (45%)
, 209.19B (60%), 181 In the same manner as in Example 1, azulene derivatives shown in Table 1 were produced. Its structure is IR-'H-NMR-113CN
Confirmed by MR- and MS-spectra.

CH3: 1340! 696 C) 13 Co41 3340.1697 CH3 3:140.1696 CH3 3340,1695 CH3 3340,1696 Coco40 1B97 CH Coco95 3340, 1696 C)+3 icH2120chlorNH-nC4HgCH CoCH Example 2 Bis(0-propyl- Production of 3-C7-isopropyl-1-methyl-azulen-4-yl)-N-(n-butyl)-urethane-squaric acid dye (compound/1627): N-(n-butyl)-0-propyl -3-[7-itubrobyl-1-methylazulene-4-yltuurethane (Example 1) 6.8 g (0,002 mol) and square acid 2
．． 3.9 (0.02 mol) in toluene/n-buta/
- # (1:1) Heated under reflux for 5 hours in 160 ml. After distilling off the solvent under reduced pressure, the green clear substance remaining was treated by chromatography on silica gel (
methylene chloride/acetone). 2.3 g (30%) of crystals with metallic luster were obtained.

Physical data: Melting point = 155-156°C UV (CH2Cl1): λmax = 770n
m(ε=112250); IR(KBr): ν=3
325 (NH), 2958.2928.2862.1
691.1609.1592.1543.1432.1
387.1326s, 124B, 1217.1024.
916.765.537 cm-';'H-NMR(
CDCl5): δ=0.84t (6H), 1
．． 16-1.45m (8H), 1.48d (12'H
), 1.91q (4H), 2.55s (6H), 2.9
8q (4H), 3.11q (2H), 5.88m (4
H), 5.98m (4H), 4.74 broad (2
NH), 7.45d (2H), 7.58d (2H), 8
．． 09s (2H), 8.82s (2H) ;”C-
NMR (CDCI, ): δ=12.96 (2C), 1
3.66 (2C), 19.95 (2C), 24.24
(4C), '31.02 (2C), 32.16 (2C
), 36.30 (2C), 58.40 (2C), 40.
9 1 (2C), 63.97 (2C), 12
1.66 (2C), 130.82 (2C), 13 B
, 98 (2C'), 134.55 (2C'), 138
．． 24 (2C), 139.85 (2C), 141.83
(2C), 147.50 (2C), 150.27 (2C
'), 156.01 (2C), 156.72 (2C)
, 179.53.182.75.183.24 (2C)
;MS: m/e = 762. ．． 760 (40%
) In the same manner as in Example 2, the square acid dyes shown in Table 2 were produced, and further IR-'H-NMR-'C-NMR- and M
Characterized by S-spectrum.

CHCH20CIOINH-C@Hs l H3 CHCH20CIOINH-nC4% CH co CHCH20CIOINH-tc, H9CH co CHCH2QCIOINH-iC3H7H3 1,) lcH20c暉→ CH co CHCH20CIOINH-nc1aH37H3 CHICH312 CHICH312 CHICH, l2 CHICH ko) 2 CHICH312 CHICH312 CHICH ko) 2 C-drawn commercial) 2 CHIC8312 1cH2120ci01NH-C4H.

H3 C) IIc) +312 CHICHs12 CHICH3h 1115-167 warehouse 04-175 warehouse +68-169 Yu 1! 17-198 store 93-74 meeting 209 meals 201-202 meal 9G-115 store so-as meeting E4-] meeting 102 meals Example 6 A 2705% by weight solution of the dye in toluene was rotated at approximately 2000 rll using a sprayer. on a polymethyl methacrylate disk containing a
Centrifugation was performed at o o rpm. Semiconductor laser (λ
= 850 nm) gave a homogeneous, highly reflective dye layer which could be written very well. This information can be read out again with good contrast.

Example 4 A 6% by weight solution of Dye 27 (which contains 60% by weight of polymethyl methacrylate relative to the content of dye dissolved in the solution) was prepared as in Example 3 in a grooved polycarbonate circle. It was applied onto the plate by centrifugation. A homogeneous highly reflective dye layer is obtained, which adheres well to the substrate, describes the grooves of the substrate well and can be written very well by a semiconductor laser (λ=830 nm). was completed. The written information is climate stable and can be read out repeatedly at will with good contrast.

Example 5 A 2702% by weight solution of dye in propatool/diacetone alcohol (1:1), which contains 10% by weight of phenolic resin as binder and 5% by weight of phenolic resin as binder, based on the content of dye dissolved in the solution. 4-octyl-4'- as a stabilizer
(contains fluoro-diphenyldithiol nickel)
was centrifugally applied onto a grooved polycarbonate disk in the same manner as in Example 6. The storage layer obtained was comparable in all respects with that from Example 3, but
It had higher stability against V rays.

Example 6 A 2% by weight solution of dye 48 in toluene, which contains 10% by weight of polymethyl methacrylate and 5% by weight of nickel biscamphalate dithiol, based on the content of dye dissolved in the solution, is It was centrifugally coated onto a glass plate in the same manner as in Example 3. The dye layer obtained was homogeneous and exhibited high basic reflectivity. This layer is a semiconductor laser (λ=
780 nm) allows better writing. The written information is stable under normal test conditions and can be read repeatedly at will.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, L is C_1~ substituted with a phenyl group as the case may be)
C_1_2-alkylene group, R^1 is C_1-C_2_
0-alkyl group, C_5-C_7-cycloalkyl group or optionally substituted phenyl group, R^2, R^3,
R^4 and R^5 may be the same or different and each independently represents a hydrogen atom or optionally a halogen atom,
C_1-C_1_2-Alkoxy group, phenyl group, substituted phenyl group, C_1-C_1_2-Alkoxycarbonyl group or C_1-C_ substituted with cyano group
1_2-Alkyl group, provided that when R^5 means a hydrogen atom, in one or both azulene rings, the substituents CH_2-L-O-CO-NHR^1 and R^
An azulene tetragonal acid dye having a urethane group represented by (the ring positions of 4 may be exchanged with each other within the azulene ring). 2, R^2, R^3, R^4 and R^5 are each C_
1-C_6-alkyl group,
The azulene tetragonal dye according to claim 1. 3, R^2 and R^4 are each a methyl group, and R^
The azulene tetragonal dye according to claim 1, characterized in that 3 and R^5 each represent a hydrogen atom. 4. The azulene quartz dye according to claim 1, wherein R^2 and R^4 each represent a hydrogen atom, R^3 represents an isopropyl group, and R^5 represents a methyl group. 5. Optical recording medium, consisting of a support and a photosensitive thin layer coating containing a dye and optionally a binder, characterized in that the dye is a dye of formula I according to claim 1. 6, R^2, R^3, R^4 and R^5 are each C_
1-C_6-alkyl group,
The optical recording medium according to claim 5. 7, R^2 and R^4 are each a methyl group, and R^
Optical recording medium according to claim 5, characterized in that 3 and R^5 each represent a hydrogen atom. 8. The optical recording medium according to claim 5, wherein R^2 and R^4 each represent a hydrogen atom, R^3 represents an isopropyl group, and R^5 represents a methyl group. 9. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, L is C_1~ substituted with a phenyl group as the case may be)
C_1_2-alkylene group, R^1 is C_1-C_2_
0-alkyl group, C_5-C_7-cycloalkyl group or optionally substituted phenyl group, R^2, R^3,
R^4 and R^5 may be the same or different and each independently represents a hydrogen atom or optionally a halogen atom,
C_1-C_1_2-alkoxy group, phenyl group, substituted phenyl group, C_1-C with C_1-C_1_2 substituted with -alkoxycarbonyl group or cyano group
Urethane group-containing azulene represented by _1_2-alkyl group.